MXPA99004816A - Composition of rubber and rim that has bearing band of the mi - Google Patents

Abstract

A method for preparing a preformed elastomer / filler compound of a diene-based elastomer and particulate filler dispersed therein by polymerizing monomers in the presence of the filler with a polymerization promoting catalyst wherein at least a portion of the catalyst is previously deposit on the filling. This previously formed elastomer composite is also contemplated as a rubber composition comprised of a mixture of said preformed compound and at least one additional elastomer. Said filler may be, for example, precipitated silica, carbon black and / or modified carbon black. Also provided is a tire having a component of said rubber compound or composition such as, for example, a rubber band.

Description

COMPOSITION OF RUBBER AND RIM THAT HAS BEARING BAND OF THE SAME FIELD This invention relates to the preparation of an elastomer composite previously formed as a diene-based elastomer and particulate filler dispersed therein by polymerizing monomers in the presence of the filler, wherein a part of the polymerization catalyst is contained in a filler. previously treated. The previously formed elastomer composite is also contemplated as well as a rubber composition containing said elastomer compound. In addition, a rim having a component, such as for example a tread, comprised of said elastomer compound or rubber composition is contemplated.

BACKGROUND Tires are typically prepared from treads of elastomer-based rubber compositions that are conventionally reinforced with carbon black. Occasionally, tread rubber and tire tread compositions are also reinforced with silica frequently with an inclusion of a coupling agent to assist in coupling the rubber backfill. Sometimes it is desired to improve a homogeneous dispersion of the reinforcing filler in the rubber composition, such as, for example, by efficient or longer mixing of the rubber composition or by other means. In accordance with patent publication WO96 / 34900, a polyolefin compound could be prepared by polymerizing olefin (s) in the presence of (i) a transition metal catalyst, (ii) co-catalyst or activator for the transition metal catalyst , and (iii) filling. The product is said to be obtainable as free flowing particles that can be processed into shaped articles, such as, for example, injection molding, rotational molding, compression molding, profile extrusion, flat die film extrusion and coextrusion. However, it is desired herein to produce elastomeric compositions containing integral reinforcing fillers. It is hereby considered that the preparation of such elastomers containing reinforcing filler is not addressed by the WO patent publication. The term "phr" if used herein, and in accordance with conventional practice, refers to "parts of a respective material per 100 parts by weight of rubber or elastomer". In the description of this invention, the terms "rubber" and "elastomer" if used herein, may be used interchangeably, unless otherwise prescribed. The terms "rubber composition", "compound rubber" and "rubber compound", if used herein, are used interchangeably to refer to "rubber that has been mixed with various ingredients and materials" and such terms they are well known to those who have experience in the technique of mixing rubber or rubber composition.

SUMMARY AND PRACTICE OF THE INVENTION In accordance with this invention, a method for preparing a diene / filler based elastomer composite, ie, a preformed elastomer containing an integral filler dispersion therein, comprises (A) polymerizing at least one conjugated diene hydrocarbon or copolymerizing at least one conjugated diene hydrocarbon and an aromatic vinyl compound in an organic solvent and in the presence of (1) polymerization promoting catalyst and (2) at least one particulate filler selected from starting at least one carbon black and precipitated silica, and (B) terminating the polymerization reaction; wherein the elastomeric compound contains from about 10 to about 100 phr of the filler; wherein the catalyst is a combination of a first co-catalyst selected from at least one of a Group 4, 5 or 6 of transition metal compound, a metallocene, a lanthanide, actinide organocobalt and organonickel compound and a second co-catalyst selected from at least one of an organoaluminum, organozinc and organomagnesium compound; and wherein the catalyst combination is provided as (i) at least one of the fillers as a pre-treated filler having the first co-catalyst on the surface thereof and the second co-catalyst being added to the monomer / mixture solvent? / filler or (ii) at least one of the fillers as a previously treated filler having the second co-catalyst on the surface thereof and the first co-catalyst added to the monomer / solvent / filler mixture. The invention further contemplates a rubber composition comprised of the preformed elastomer / filler composite of this invention and a diene-based elastomer.

The invention additionally contemplates a rim having at least one component comprised of said elastomer compound or said rubber composition. The invention additionally contemplates said rim having a tread comprised of said elastomer compound or said composition. of carbon for this invention is a carbon black reinforcing rubber, as would be understood by one having experience in the field of rubber composition. Examples of such carbon blacks are described in The Vanderbilt Rubber Handbook, 13th Edition, and pages 417-418. In another aspect of the invention, the modified carbon black filler is said carbon black which has been treated to contain at least one fraction selected from silanol, siloxane, titanium oxide, titanium hydroxide, zircomo oxide, hydroxide zirconium and aluminum hydroxide groups on the surface thereof Modified carbon blacks are also contemplated as carbon blacks containing at least one of the groups of polysulphide of aplo, polysulfide of alkyl, thiol, thiophenol, epoxide, aillo and vinyl on the surface thereof. Representative polysulfide groups are, for example. dibenzyl disulfide and ditolyl disulfide. Representative alkyl polysulfide groups are, for example, bis (propi) disulfide and bis (propyl) tetrasulfide. Representative thiol groups are, for example, n-propyl thiol and n-butyl thiol. It is representative of the thiophenol groups, for example, orthomethylthiophenol. The representative epoxide groups are. for example, n-propyl epoxide and n-butyl epoxide. Representative allyl groups are, for example, methylallyl and propylallyl groups. Representative vinyl groups are, for example, ethylvinyl and propylvinyl groups. For the preparation of the previously formed / filled elastomeric compound of this invention, conjugated dienes such as isoprene and 1,3-butadiene are representative of diene monomers. Representative of the aromatic vinyl compounds are styrene and alpha-methylstyrene, preferably styrene. Also, for the rubber composition of this invention comprised of the preformed / filled elastomer composite and at least one additional elastomer, the additional elastomer is preferably selected from homopolymers and copolymers of said dienes and copolymers of one or more of said dienes and an aromatic vinyl compound are contemplated. It should be noted that additional carbon black and / or silica can be used in the preparation of said rubber composition wherein at least one additional elastomer is used with the previously formed / filled elastomeric compound to form the rubber composition, for this invention, the diene-based elastomers (rubbers) prepared from said monomers are also contemplated for the rubber compositions for the elastomer / rubber compound mixture. In another aspect of this invention, the diene-based elastomer can be tin or coupled silicone. Historically, aluminum / magnesium / titanium based catalysts are used to polymerize monoolefins to form thermoplastic polymers such as, for example, polyethylene. However, for the preparation of the previously formed elastomeric compound, it is considered herein that said catalyst combination would be inappropriate. It should be noted that it is an important aspect of this invention for the preparation of the preformed / filled elastomer composite that a polymerization catalyst component be provided as a previously treated filler compound. In the practice of this invention, the previously treated filler compound is a filler containing the first or second co-catalyst on its surface. Said filler compound can be obtained, or pretreated, for example, by mixing a dehydrated filler in an organic diluent with a first or second co-catalyst, as the case may be, followed by drying the resulting filler compound. The stuffing can be dehydrated by conventional means well known to those experienced in the art. While various polymerization catalysts may be used, or catalyst systems for polymerizing the diene monomers to form a diene-based elastomer primarily, the preferred catalysts are (1) Ziegler-Natta type of catalyst and (2) metallocene-type catalysts. they prefer These catalysts and their use to polymerize diene-based monomers to form elastomers are well known to those having experience in that field. Representative examples of one type of Ziegler-Natta catalyst can be found, for example, in publications such as Textbook of Polymer Science, by F. W. Bill eyer Jr. For the first co-catalyst, representative examples of transition metal compounds of Group 4, 5 or 6 are, for example, titanium, vanadium, niobium and chromium halides. Chlorine is a preferable halide. Representative of said compounds are, for example, titanium chloride (titanium tetrachloride), vanadium chloride, niobium chloride and chromium chloride. The first additional co-catalysts can include imido tri (neopentyl) molybdenum as well as organocobalt and organonickel compounds. They are composed of organocobalt and organonickel compounds, for example, cobalt octanoate and nickel octanoate. For the first co-catalyst, representative examples of a lanthanide are, for example, neodymium chloride, neodymium alkoxide, cerium chloride and ytterbium chloride. For the first co-catalyst, a representative example of an actinide is, for example, uranyl dichloride. For the first co-catalyst, representative examples of a type of catalyst metallocene can be found, for example in Metallocene Catalized Polymers published by Plastics Design Library-The Society of Plastics Engineers (1998). Representative of metallocene catalysts are, for example, cyclopentadienyl titanium dichloride, aluminum dialkylchloride, cyclopentadienyl and cobalt (dimethyl) trialkyl phosphite. For the second co-catalyst, representative examples are, for example, organoaluminum compounds, for example, trialkyl alkylaluminum, dialkylaluminium halide and alkylaluminum trihalide, particularly when the alkyl groups are selected from at least one of the methyl, ethyl groups and butyl and the halide is chlorine. For example, said organoaluminum compounds may be triethylaluminum, tributylaluminum, trimethylaluminum, ethylaluminum dichloride and triisobutylaluminum. For the second co-catalyst, additional examples are dialkylzinc and butyl magnesium chloride. In this invention, for the use of a diene polymerization promoting catalyst in the presence of a selected filler, the type of binding to the filler surface, even though it may not be fully understood, is contemplated to be: 1. Co-catalyst which promotes a direct covalent bonding activity with the surface of the filling, particularly with active groups on the surface of the filling. An example of such an approach can be found, for example, in Agne. Chem, vol. 108, page 2979 (1995). It may be exemplary of a representation of said filler surface activity, for example, when a portion of the surface of the filler itself is represented by a silanol group and wherein the catalyst component is, for example, tri (neopentyl) molybdenum imide. 2. Adsorption of first co-catalyst towards the filling surface. By this method, a further reaction uses a second co-catalyst, which is added together with the monomer to the polymerization system, to convert an adsorbed species of cobalt, nickel neodymium, and / or titanium to the active catalyst system. 3. Alternatively, a second co-catalyst is adsorbed to the filler surface and the first co-catalyst added together with the monomer in the polymerization system to complete an active catalyst formation. The polymerization could be conducted, for example, in the following manner: (1) dehydrating the filler in an appropriate oven at a temperature of about 200SC for about 2 hours, (2) mixing the dehydrated filler with an organic hydrocarbon solvent such as , for example, toluene, pentane, hexane and / or heptane, to create a dispersion therein, (3) by adding a first or second co-catalyst, as the case may be, and allowing it to react with hydroxyl groups contained on the surface of the filling to form the filler compound of this invention, followed by (4) addition of a diene hydrocarbon monomer and first or second co-catalyst, as the case may be, (5) to allow a polymerization of the monomer to proceed and form an elastomeric polymer, (6) stop the polymerization reaction by addition of a monoalcohol, such as for example, methanol and cooling the polymerized, and then (7) recovering the diene-based elastomeric polymer compound by filtration and drying the recovered elastomer under vacuum (reduced pressure) for eliminate the solvent. It is intended that the product be recovered as an elastomeric composition containing an integral filler dispersion therein. In the practice of this invention, a silica coupler can be used to couple the silica, and optionally the modified carbon black, to one or more than the elastomers in the rubber composition This silica coupler conventionally has a fraction, preferably a silane fraction, reactive with (i) at least one of the fractions on the surface of the modified carbon black, and (n) with silanol groups on the silica, if the silica is used, and another interactive fraction with at least one of the elastomers. Bis-3- (trialkoxysilylalkyl) polysulfides are typical of these coupling agents. Representative of these are, for example, bis-3- (triethoxysilylpropyl) polysulfide having an average of about 2.1 to about 4 sulfur atoms in its polysulfide bridge. Also, in the practice of this invention, while contemplating the use of various elastomers as discussed above, these elastomers may be selected, for example, from at least one of cis 1-polyisoprene rubber (natural and / or synthetic and preferably natural rubber), 3, 4-polyisoprene rubber, styrene / butadiene copolymer rubbers, isoprene / butadiene copolymer rubbers, styrene / isoprene copolymer rubbers, styrene / isoprene / butadiene terpolymer rubbers, rubber cis 1, 4-polybuta-diene, 1, 4-polybutadiene trans rubber (70-95 percent trans), low vinyl polybutadiene rubber (10-30 percent vinyl), medium vinyl polybutadiene rubber ( 30-50 percent vinyl), and high vinyl polybutadiene rubber (50-90 percent vinyl). The vulcanized rubber composition should contain a sufficient amount of the previously formed / filled elastomer composite, usually at least about 30, and usually greater than about 40 phr, to contribute to a reasonably high modulus, high abrasion resistance and strength to tear for the cured rubber composition. In the practice of this invention, the silica may be present at levels less than about 100 phr such as, for example, about 10 to about 90 phr, or nothing at all. The commonly used silicon pigments used in rubber composition applications can be used as the silica in this invention, including pyrogenic and precipitated siliceous pigments, including aluminosilicates, even though precipitated silicas are usually preferred. The silicious pigments preferably used in this invention are precipitated silicas, such as, for example, those obtained by the acidification of a soluble silicate, e.g., sodium silicate, generally exclusive of silica gels. These silicas could be characterized, for example, by having a BET surface area, as measured using nitrogen gas, preferably in the range of about 40 to about 600, and more usually on a scale of about 50 to about 300 meters. square per gram (m2 / g). The BET method of measuring surface area is described in the Journal of, the American Chemical Society, Volume 60, page 304 (1930). The silica can also typically be characterized having an absorption value of dibutyl phthalate (DBP) on a scale of about 100 to about 400., and more usually around 150 to about 300 cc / 100 gr. The silica could be expected to have an average final particle size, for example, on the scale of 0.003 to 0.05 microns as determined by electron microscopy, even though the silica particles may be even smaller, or possibly larger, in size. It can also be expected that the silica has mercury porosimetry characteristics such as, for example, HgSSA on a scale of about 50 to about mVg, a V (Hg) on a scale of about 1 to about .5 cmVg and a maximum of PSD between 10 to about 50 nm. Various commercially available silicas can be considered for use in this invention, such as, for example only and without limitation, silicas commercially available from PPG Industries under the trademark Hi-Sil with designations 210, 243, etc.; available silicas from Rhone-Poulenc, for example, with designations of Zeosil 1165MP and silicas available from Degussa AG, with designations, for example, VN2 and VN3, BV3380GR, etc., and Huber as Zeopol 8745. It is easily understood by those who they are skilled in the art that the rubber composition would be composed by methods generally known in the rubber composition art, such as by mixing the various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, curing aids, as sulfur, activators, retarders and accelerators, processing additives, such as oils, resins including tackifying resins, silicas and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents and materials reinforcement such as, for example, carbon black. As is known to those skilled in the art, depending on the intended use of the vulcanizable material with sulfur and vulcanized with sulfur (rubbers), the aforementioned additives are commonly selected and used in conventional amounts. Carbon blacks of reinforcing type can also be added to the rubber composition, depending somewhat on the desired physical properties and intended use of the rubber composition. It should be noted that the silica coupler and / or the silica silylating agent, if in liquid form, can be used in conjunction with a carbon black carrier, ie, pre-mixed with a carbon black prior to the addition to the rubber composition, and said carbon black should be included in the aforementioned amount of carbon black considered in the rubber composition formulation. Typical amounts of tackifying resins, if used, comprise about 0.5 to about 10 phr, usually about 1 to about 5 phr. Typical amounts of processing aids comprise about 1 to about 50 phr. These processing aids may include, for example, aromatic, naphthenic, and / or paraffinic processing oils. Typical amounts of antioxidants comprise about 1 to about 5 phr. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others such as, for example, those described in The Vanderbilt Rubber Handbook (1978), pages 344-346. Typical amounts of antiozonants comprise about 1 to 5 phr. Typical amounts of fatty acids, if used, which may include stearic acid, palmitic acid, linoleic acid or mixtures of one or more fatty acids, may comprise from about 0.5 to about 3 phr. Stearic acid is often used in a relatively impure state and is commonly referred to in the rubber composition practice as "stearic acid" and is so called in the description and practice of this invention. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr. Microcrystalline waxes are often used. Typical amounts of peptizers, if used, comprise about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide. The vulcanization is conducted in the presence of a sulfur vulcanization agent. Suitable sulfur vulcanization agents include elemental sulfur (free sulfur) or sulfur donor vulcanizing agents, for example, an amine disulfide, polymorphic disulfide or sulfur olefin adducts. Preferably, the sulfur vulcanization agent is elemental sulfur. As is known to those skilled in the art, sulfur vulcanization agents are used in an amount ranging from about 0.5 to about 4 phr., or even, in some circumstances, up to about 8 phr, with a scale of about 1 to about 2.5, sometimes from about 1 to about 2, being preferred. The accelerators are used to control the time and / or temperature required for vulcanization and to improve the vulcanization properties. In one embodiment, a single accelerator system, ie primary accelerator, can be used. Conventionally and preferably, a primary accelerator (s) is used in total amounts ranging from about 0.5 to about 4, preferably about 0.8 to about 2 phr. In another embodiment, combinations of a primary and a secondary accelerator can be used with the secondary accelerator being used in amounts of about 0.05 to about 3 phr in order to activate and improve the properties of the vulcanizate. It could be expected that the combinations of these accelerators produce a synergistic effect on the final properties and be somewhat better than those produced by the use of any single accelerator. in addition, the delayed action accelerators can be used which are not affected by the normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders can also be used. The appropriate types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurases, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiuram compound. The presence and relative amounts of sulfur vulcanization agent and accelerator (s) are not considered as an aspect of this invention that is more primarily directed to the use of the prescribed silylating agent in combination with a silica coupler in a reinforced rubber composition. with silica. The presence and relative amounts of the other additives, as described above, are not considered as an aspect of the present invention that is more primarily directed to the use of the prescribed preformed elastomer / filler compound. The ingredients are mixed typically in at least two stages, say, at least one non-productive stage followed by a productive mixing stage. The final curatives are typically mixed in the final stage which is conventionally referred to as the "productive" mixing stage wherein the Mixing typically occurs at a temperature, or final temperature, lower than the mixing temperatures of the preceding non-productive mixing stages. The rubber, silica, silica coupler, silica silage agent and carbon black, if used, are mixed in one or more non-productive mixing stages. The terms "non-productive" and "productive" mixing stages are well known to those who have experience in the field of rubber mixing. In at least one of the stages of non-productive mixing (NP), the materials are mixed thermomechanically and the mixing temperature is allowed to reach a temperature between 140aC and 190eC. The rubber composition of this invention can be used for various purposes. For example, it can be used for various rim compounds. These rims can be constructed, shaped, molded and cured by various methods that are well known and will be readily apparent to those who have experience in that field. The invention can be better understood by reference to the following examples in which the parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1, For this Example, a preformed elastomer / dispersed filler composite is prepared as follows. A pretreated filler is prepared by first dehydrating silica precipitated to particles such as Zeosil 1165 MP from Rhone Poulenc, in an oven for about two hours at a temperature of about 200aC, the dehydrated silica is then cooled to about 23SC and mixed, in a heptane solvent. A second co-catalyst of tri-ethyl aluminum is added and allowed to react with silanol group on the surface of the silica. To the silica / catalyst compound dispersion in the organic solvent is added 1,3-butadiene monomer together with a first cobalt octanoate co-catalyst. The polymerization is allowed to proceed for about 1.5 hours at about 65 ° C to about 80 percent completion of the polymerization reaction. The polymerization was stopped with the addition of metal and the resulting polymerization was cooled to about zero aC and the elastomer / filler compound was then recovered by drying at a temperature of about 23aC. The resulting styrene / butadiene copolymer elastomer has a cis 1,4- content of about 90 percent and contained about 30 weight percent of silica integrally dispersed therein.

EXAMPLE II An elastomer composition is prepared by mixing about 50 phr of the preformed / filled elastomeric compound of Example 1 with about 60 phr of an additional organic solution prepared by polymerization of the rubber composition and styrene / butadiene elastomer ingredients, which included stearic conventional amounts of zinc oxide and acid for about 6 minutes at a temperature of about 160 ° C. Then, sulfur and vulcanization accelerators are mixed with the resulting composition for about 2 minutes at a temperature of about 120 ° C. The resulting rubber composition is cured for about 14 minutes at a temperature of about 160SC. Although certain embodiments and representative details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without abandoning the spirit or scope of the invention.

Claims (17)

1. - A method for preparing a diene based elastomer compound characterized in that it contains a particulate filler dispersion therein, comprises (A) polymerizing at least one conjugated diene hydrocarbon or copolymerizing at least one conjugated diene hydrocarbon and a compound of aromatic vinyl in an organic solvent and in the presence of (1) polymerization promoting catalyst and (2) at least one particulate filler selected from at least one of carbon black and precipitated silica and (B) finishing the polymerization reaction; wherein the elastomeric compound contains from about 10 to about 100 phr of the filler; wherein the catalyst is a combination of a first co-catalyst selected from at least one of a transition metal compound of Group 4, 5 or 6, a metallocene, a lanthanide, actinide, organocobalt and nickel organ compound and a second co-catalyst selected from at least one of an organoaluminum, organozinc and organomagnesium compound; and wherein the catalyst combination is provided as (i) at least one of the fillers as a pretreated filler having the first co-catalyst on the surface thereof and the second co-catalyst being added to the monomer mixture / solvent / filler or (ii) at least one of the fillers as a previously treated filler having the second co-catalyst on the surface thereof and the first co-catalyst being added to the monomer / solvent / filler mixture.

2. The method of claim 1, wherein the filler is carbon black.

3. The method of any of the preceding claims 1 and 2, characterized in that the carbon black is a carbon black reinforcing rubber, modified having at least one fraction selected from the groups of silanol, siloxane, oxide of titanium, titanium hydroxide, zirconium oxide, zirconium hydroxide and aluminum hydroxide on the surface thereof.

4. The method of any of the preceding claims 1 and 2, characterized in that the carbon black contains at least one of the groups of aryl polysulfide, alkyl polysulfide, thiol, thiophenol, epoxide, allyl and vinyl on the surface of the same.

5. The method of any of the preceding claims 1 and 2, characterized in that the carbon black contains at least one of the groups of dibenzyl disulfide, ditolyl disulfide, bis (propyl) disulfide, bis (propyl) tetrasulfide ), n-propyl thiol, n-butyl thiol, ortho-ethylthiophenol, n-propyl epoxide, n-butyl epoxide, methylallyl, propylallyl, methylvinyl and propylvinyl on the surface thereof.

6. The method of any of the preceding claims 1 and 3-5, characterized in that the filler is a precipitated silica.

7. The method of any of the preceding claims, characterized in that the previously treated filler is prepared by solvent deposition of the first co-catalyst on the dehydrated carbon black filler.

8. - The method of any of the preceding claims 1-6, characterized in that the treated filler is prepared by solvent deposition of the second co-catalyst on a dehydrated carbon black filler.

9. The method of any of the preceding claims, characterized in that the previously treated filler is prepared by solvent deposition of the first co-catalyst on a dehydrated silica filler.

10. The method of any of claims 1-6 above, characterized in that the treated filler is prepared by solvent deposition of the second co-catalyst on a precipitated, dehydrated silica filler.

11. The method of any of the preceding claims, characterized in that the first co-catalyst is selected from at least one of halides of titanium, vanadium, niobium and chromium.; imido tri (neopentyl) molybdenum, neodymium chloride, cerium chloride, ytterbium chloride, uranyl dichloride, cyclopentadienyltitaniol dichloride, aluminum dialkylchloride, cyclopentadienilyl and cobalt (dimethyl) trialkyl phosphite.

12. The method of any of the preceding claims 1-10, characterized in that the first co-catalyst is selected from at least one of titanium chloride, vanadium chloride, niobium chloride, chromium chloride, octanoate of cobalt and nickel octanoate.

13. The method of any of claims 1-10 above, characterized in that the second co-catalyst is at least one of an organoaluminum compound selected from alkylaluminum trialkyl, dialkylaluminum halide or alkylmagnesium trihalide; wherein the alkyl groups for the organoaluminum compound, dialkyl zinc and alkylmagnesium halide are selected from one of the group consisting of methyl, ethyl and butyl groups,

14. The method of any of the preceding claims 1-10 , characterized in that the second co-catalyst is selected from at least one of triethylaluminum, tributylaluminum, trimethylaluminum, ethylaluminum dichloride, triisobutylaluminum, dialkylzinc and butylmagnesium chloride.

15. The method of any of the preceding claims, characterized in that the conjugated diene is selected from at least one of isoprene and 1,3-butadiene and the aromatic vinyl compound is selected from at least one of styrene and alpha-methylstyrene.

16. A previously formed / filled elastomer composite, characterized in that it is prepared by the method of any of the preceding claims.

17. A rubber composition characterized in that it is comprised of the preformed / filled elastomer composite of claim 16 and at least one additional elastomer selected from homopolymers and copolymers of at least one diene hydrocarbon and copolymers of at least one Diene hydrocarbon and an aromatic vinyl compound, 18, - The rubber composition of claim 17, characterized in that the diene hydrocarbon is selected from at least one of the group consisting of isoprene and 1,3-butadiene and the aromatic vinyl compound is styrene. 19. A rim having a component comprised of the rubber composition of any of claims 17 and 18 above. 20. A tire having a tread comprised of the rubber composition of any of claims 17 and 18 above.